CA1231716A - Acaricidal ester of tricyclohexyl-tin hydroxide - Google Patents
Acaricidal ester of tricyclohexyl-tin hydroxideInfo
- Publication number
- CA1231716A CA1231716A CA000449971A CA449971A CA1231716A CA 1231716 A CA1231716 A CA 1231716A CA 000449971 A CA000449971 A CA 000449971A CA 449971 A CA449971 A CA 449971A CA 1231716 A CA1231716 A CA 1231716A
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- Canada
- Prior art keywords
- tricyclohexyl
- plants
- act
- tin
- acaricidal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
- A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
- A01N55/04—Tin
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/22—Tin compounds
- C07F7/2224—Compounds having one or more tin-oxygen linkages
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT
"ACARICIDAL ESTER OF TRICYCLOHEXYL-TIN HYDROXIDE"
Tricyclohexyl-tin benzoate, a process for its preparation, acaricidal and insecticidal compositions which comprise it as active ingredient and the use of such compositions to prevent damage to plants by phytophagous insects and acarids, are described.
"ACARICIDAL ESTER OF TRICYCLOHEXYL-TIN HYDROXIDE"
Tricyclohexyl-tin benzoate, a process for its preparation, acaricidal and insecticidal compositions which comprise it as active ingredient and the use of such compositions to prevent damage to plants by phytophagous insects and acarids, are described.
Description
~ 23 1 7 1 ~
"ACARICIDAL ESTER OF TRICYCLOHEXYL-TIN HYDROXIDE"
The present invention relates to a new organic derivative of tin, a method for its preparation,insecticidal and acaricidal compositions containing this derivative and a method of treating plants with these compositions to protect them from phytophagous insects and acarids.
Tricyclohexyl-tin hydroxide, better known by its common name cyhexatin, is a known acaricide which is noteworthy for its specific activity against phytophagous acarids, in particular in arboriculture and in the 10 cultivation of vegetables and ornamental plants. This product is used in the form of a wettable powder and, more recently, an emulsifiable concentrate. However, this latter formulation is difficult to prepare because of the -insolubility of cyhexatin in most of the usual solvents used 15 in agrochemistry. Complicated emulsifier systems, which do not ensure that the formulation has a completely satisfactory stability, have thus had to be used.
The present invention provides a new organic derivative of tin, which also has an excellent acaricidal 20 activity and moreover, surprisingly, can very easily be formulated in the form of an emulsifiable concentrate because of its remarkable solubility in the usual solvents used in agrochemistry.
The new organic derivative of tin according to 25 the present invention is tricyclohexyl-tin benzoate.
1 2 3 1 7 ~ B
The present invention also provides acaricidal compositions containing this product as the active ingredient, and in particular emulsifiable concentrates, which can be used to treat plants against phytophagous acarids.
Tricyclohexyl-tin benzoate has the formula:
( O ) - Sn - 0 - ~ - ~ (I) It can be prepared, for example, by reacting benzoic acid on tricyclohexyl-tin hydroxide. This reaction is carried out in an inert organic solvent medium, such as toluene, xylene, chlorobenzene, polychlorobenzene or cyclohexanone, at a temperature of, in general, at most 60C. The water formed in the course of the reaction is preferably removed at the rate at which it is formed, for example by absorption with a water-soluble salt, such as sodium sulphate or magnesium sulphate, or by azeotropic distillation of the solvent/water mixture.
The isolated product obtained is in the form of a white crystalline powder of melting point 111C.
The following non-limitative examples illustrate the invention.
i ~ 3 ~
i Example 1 A 20 l;tre reactor ;s charged with tr;cyclohexyl-tin hydrox;de (2"326 9, 6.04 mol), anhydrous toluene (9 l;tres) and benzo;c ac;d t737 9, 6.04 mol). The mix-5 ture ;s heated at about 50 - 60C, w;th st;rr;ng, for 1 hour 30 m;nutes and cooled to room temperature. Anhydrous sod; um sulphate (1,500 9) ;s then added and st;rr;ng ;s cont;nued for 1 hour The mixture ;s f;ltered and the f;ltrate ;s concentrated under redused pressure (6 mm Hg =
lO 789 Pa) at 50C. A wh;te sol;d product prec;pitates and ;s recrystall;sed ~rom hexane t3,250 ml) at 50C. The pro~
duct prec;p;tates by cooling to 10 - 15C. It ;s dr;ed and r;nsed ~;th cold hexane (750 ml). After dry;ng ;n a dry-;ng oven at 30C under reduced pressure t6 mm Hg = 789 Pa), 15 tr;cyclohexyl-t;n benzoate (2,185 g) ;s thus obta;ned.
~he hexane f; ltrate ;s concentrated and a second portion of product (362 9) is obta;ned.
- Total weight obta;ned: 2,547 9 - Y;eld: 36.8 X
20 ~ Melt;ng point: 111C
The structure shown ;s conf;rmed by analys;s by ;nfrared and proton NMR spectrometry.
Example 2 An emuls;f;able concentrate hav;ng the follow;ng 25 compos;t;on, for one l;tre of formulation, is prepared:
i23`17~
.
- tricyclohexyl-t;n benzoate 411 9 - calc; um dodecylbenzenesulphonate ;n 60X strength solution in isopropanol 50 - a 30 - 33: 1 ethylene ox;de/castor o;l condensate 50 9 - xylene 498 9 specif;c gravity at 20C: 1.008 Example 3 A reactor is charged, with cycloh~xanone (546 9) lO and 94 % pure tricyclohexyl-tin hydroxide (316 9) at 50C, w;th st;rring. The t;n derivat;ve does not dissolve.
Benzo;c ac;d (95 9) ;s then added and the temperature ;s kept at 50C. After st;rr;ng for 10 m;nutesr a yellow solut;on ;s obta;ned ~h;ch, after f;ltration and drying, 15 gives a clear solut;on. An emuls;f;able concentrate of spec;f;c grav;ty 1.057 at 20C ;s obta;ned by add;ng emuls;f;ers as ;n the preced;ng example.
Example 4 By proceeding as described in Example 2,a similar 20 emulsifiable concentrate is prepared, starting from the follow;ng m;xture:
- tr;cyclohexyl-t;n benzoate 411 9 - acetophenone 285 9 - xylene 279 9 - calc; um dodecylbenzenesulphonate ;n 60X strength solut;on ;n ;sopropanol 50 9 - ` !233716 - a 30 - 33 : 1 ethylene oxide/castor oil condensate 50 9 An emul~ifiable concentrate of specific gravity 1.075 at 20C is obtained.
5 Exa_ple 5 Acaricidal tests Bean plants at the stage of 1 trifoliate leaf are contaminated with a mixed population of Tetranychus urticae.
After 48 hours, the contaminated plants are lO treated with aqueous dilutions of the compositions to be tested, using a spray gun of the FISCHER type, until dripping wet. These compositions consist ofo a) for reference, a commercial composition PLICTRAN 600 F*, i.e. a concentrated aqueous suspension of 600 g/litre of 15 cyhexatin, and b) the emulsifiable concentrate according to the invention obtained in Example 3.
Three bean plants are used per product and per dose. The treated plants are kept in a greenhouse for 14 20 days (temperature 20-25C, relative humidity 40-60~, illumination 5 to lO,OOC lux). The plants are watered at the foot, to avoid any washing off of the products.
After 2, 7 and 14 days after the treatmentJ the population of acarids present on each plant is estimated in 25 relation to the mean of 3 controls treated only with water.
A percentage activity is deduced therefrom:
* Registered Trade Mark.
.....
1 ~ 3 ~ 7 J ~
Population on the treated plant Example: 100 X ~ in %
Populat;on on the untreated plant Under these conditions, the results shown in the following table are found:
X activity at Act;ve ingredient n days Product in g/hl 2 7 14 lO Reference 15 70 90 100 Invention 15 80100 100 15 Control 0 0 0 0 Furthermore, no phytotoxicity was found.
If the test is carr;ed out ;n the same manner on another species of acarids, Polyphagotarsonemus, it is found that the lethal dose at 90X, in ppm, ;s 10 for tri-20 cyclohexyl-t;n benzoate, ;.e. eight times less than that for the reference cyhexatin (used as a wettable powder).
Example 6: Insect;c;dal test D;scs of leaf from turnip plants are placed in gelose in Petri dishes. In each dish, 10 Plutella xyli-25 stella larvae are placed on each disc and the dish is J 2 3~ 7 1 6 covered with a ventilated lid. The product to be tested isdissolved in a water~acetone 50/50 mixture and Lhe discs are treated by spr~ying with this solution by usin~ a Potter tower at a dose equivalent to 675 litres/haO The discs S are kept at 26C. After48 hours after the treatmer,t, the l;ve and dead larvae are counted and the mortal;ty percent-age ;s calculated.
Under these conditions, it is found that tricyclo-hexyl-tin benzoate causes a mortality of at least 95% at 10 a dose of 100 g/hl, whilst cyhexatin, taken as a reference in the form of a wettable powder, is virtually inactive (less than 10%) at the same dose.
These examples clearly show:
the remarkable solubility of the compound according to the 15 invention which enables it to be easily introduced into formulations of the emuls;fiable concentrate type and enables it to be combined with other active ingred;ents of agrochem;stry, the excellent acaricidal activity of the compound accord-20 ing to the invention, which is more mult;valent than thereference, and a complementary insecticidal activity which the reference does not possess.
This compound can thus be used to combat ;nsects, 25 and more particularly phytophagous acarids, in crops such as, in part;cular, vineyards, arboriculture, vegetable crops and ornamental plants.
J ~ ~11 7 1 6 It is advantageously applied at application rates of O.05 to 5 kg/ha, preferably 0.1 to 2 kg/ha.
For its use in practice, the compound according to the invention is rarely employed by itself. Most frequently, it is used in compositions. These eompositions, which can be used to proteet plants from fungicidal diseases, eontain, as the aetive ingredient, the compound according to the invention as deseribed above in eombination with solid or liquid earriers whieh are acceptable in agricultural and/or sur~aee-aetive agen~ which are also acceptable in agriculture. In partieular, the usual inert carriers and the usual surface-active agents can be used.
These compositions can also contain any other type of ingredient, sueh as, for example, proteetive colloids, -adhesives, thickeners, thixotropie agents, penetration agents, stabilisers, sequestering agents and the like, as well as other known aetive ingredients with pesticidal properties (in partieular fungieides or, more espeeially, inseetieides) or with plant growth-promoting properties (in partieular fertilizers) or with plant growth-regulating properties. More generally, the eompounds aeeording to the invention ean be eombined with all solid or liquid additives in aecordanee with the eonventional teehniques of formulation.
In general, eompositions eontaining 0.5 to 5,000 ppm of active substanee are very suitable; these values are given for ready-to-use eompositions. "ppm" means v:~
1~1716 "parts per m;ll;on"D The range from 0.5 to 5,000 ppm corresponds to a range of from 5 x 10 5 X to 0.5 X (per-centages by weight).
As regards compositions su;table for storage and transportat;on, these more advantageously conta;n 0.5 to 95X (by we;ght) of act;ve substance.
The compos;tions to be used in agriculture accord-ing to the ;nvent;on can thus contain the act;ve ;ngred-;ents accord;ng to the ;nvent;on w;th;n very w;de limits, lO ;.e. of from 5.10 5 X to 95X (by we;ght).
In accordance w;th the above statements, the com-pounds according to the ;nvent;on are generally comb;ned with carr;ers and, ;f appropr;ate~ surface-active agents.
In the present account, the term "carrier" denotes 15 an organic or ;norgan;c, natural or synthet;c material with which the active ingredient ;s comb;ned in order to ~acil;tate its app~ication to the p~ant, to seeds or to the soil. This carrier is therefore generally inert and it must be acceptab~e in agriculture, in particular on 20 the plant treated. The carrier can be solid (clays, natural or synthet;c sil;cates, s;l;ca, res;ns, waxes, sol;d fert;l;sers and the l;ke) or l;qu;d (water, alcoholsr ketones, petroleum fractions, aromat;c or paraffinic hydrocarbons, chlorohydrocarbons, liquefied gases and the 25 l;ke).
The surface-active agent can be an emulsify;ng, d;spers;ng or wetting agent of the ion;c or non-;on;c 7 ~ ~
~ 10 --type. Examples which may be ment;oned are polyacryLic acid salts, lignosuLphonic acid salts, phenylsulphonic or naphthalenesulphonic acid salts, polycondensates of ethylene o~ide w;th fatty alcohols, fatty acids or fatty amines, subst;tuted phenols (in particular aLkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (in particular alkyltaurates) and phosphoric acid esters of polycondensates of ethylene oxide with alcohoLs or phenoLs. The presence of at least one surface-active agent is generally essential, ;f the active ingredient and/or the inert carrier are not soluble in water and if the veh;cle of appLication is ~ater.
For its application, the compound of the invent;on is thus generally in the form of compositions; these com-positions according to the invention are themselves in a fairly wide variety of solid or liquid forms.
As forms of sol;d compos;t;ons, there may be men-tioned powders for dusting or d;spersion ~with a content of compound of the formula (I) which can range up to 1û0%) and granules, ;n particular those obtained by extrusion, by compact;ng, by impregnation on a granular carrier or by granulation of a powder (the content of compound of the formula (I) in these granules is between 1 and 80%
in the latter cases).
As forms of Liquid compositions or compositions which are to be made up into liquid compositions on 1 2 ~ 1 7 ~ E
:
appl;cat;on, there may be mentioned solut;ons, in particu-lar emuLs;f;able concentrates, ultra-low volume (or ULV) formulat;ons~ emuls;ons, suspens;on concentrates, aerosols, wettable powders tor spray;ng powder) and pastes.
The emuls;f;able concentrates most frequently compr;se 10 to ~OX of act;ve ;ngred;ent, and the ready-to-use emuls;ons or solut;ons conta;n 0.01 to 20% of act-;ve ;ngred;ent~ In add;t;on to the solvent, the emuls;-f;able concentrates may conta;n, where necessary, 2 to 10 ~0% of su;table addit;ves, such as stab;~;sers, surface-act;ve agents, penetrating agents, corrosion inh;b;tors~
dyestuffs and adhes;vesO The follow;ng ;s an example of the compos;t;on of some concentrates: Exam~le 7 - act;ve ;ngred;ent 400 g/litre 15 - alkal; metal dodecylbenzenesulphonate 24 g/litre - 10 : 1 ethylene oxide/nonylphenol condensate 16 g/litre - cyclohexanone 200 g/l;tre - aromat;c solvent q.s.p. 1 litre 20The follow;ng are used in another formulat;on of an emuls;f;able concentrate: ExamE~le 8 - active ;ngredient 250 9 - epoxid;sed vegetable o;l 25 9 - m;xture of alkylaryl sulphonate and a 25 polyglycol/fatty alcohol ether100 9 - d;methylformamide 50 9 - xylene 575 9 1 ~ 3 ~
The following are used in another formulation of an emuls;fiable concentrate:~xam ~
- act;ve ingredient 450 9 - condensat& of ethylene ox;de w;th tr;styrylphenol 50 9 - alkali metal dodecylbenzenesulphonate 50 9 - chlorobenzene q.s.p. 1 litre From these concentrates, emuls;ons of any des-ired concentration can be obta;ned by d;lut;on ~;th water, these being part;cularly su;tabLe for appl;cation to the leaves.
For application called "ultra-low volume" (U.L.V.) w;th a spray of very f;ne droplets, solut;ons ;n organ;c solvents contain;ng 70 to 99 % oF act;ve ;ngredient are 15 prepared.
An ultra low volume formulat;on ;s prepared, for example, ~ith the following composition: Example 10 - act;ve ingre~;ent 200 9 - paraff;n;c/aromat;c o;l 200 9 20 - aromat;c solvent q.s.p. 1 l;tre The follow;ng is another ultra-low volume formul-at;on Example 11 .
- tr;cyclohexyl-t;n benzoate 150 9 - cypermethr;n 30 9 25 - tr;azophos 125 9 - paraffinic/aromatic oil 150 9 - betapinene 19 9 ~3~L7~L~
! . - 13 - acet;c anhydr;de 15 3 - cyclohexanone q.s.p. 1 litre The suspension concentrates, which can also be appl;ed by spraying are prepared so as to g;ve a stable fluid product wh;ch does not form a depos;t~ and they usually conta;n from 10 to 75 X of act;ve ;ngred;ent, from ~.5 to 15 % of surface-act;ve agents, from 0.1 to 10X of th;xotrop;c agents, from 0 to 10 X of su;table add;t;ves, such as ant;-foam agents, corros;on ;nh;b;tors, stabil;sers, penetrat;ng agents and adhes;ves, and, as the carr;er, water or an organic liqu;d ;n ~h;ch the act-;ve ;ngred;ent ;s spar;ngly soluble or ;nsoluble: certa;n sol;d organ;c substances or ;norgan;c salts can be d;s-solved ;n tne carr;er ;n order to ass;st ;n prevent;ng sed;-~5 mentat;on or to act as ant;-freeze agents for the water.
The wettable po~ders (or spray;ng powder) are usually prepared so as to conta;n 20 to g5% of act;ve ;ngredient, and they usually conta;n, ;n addit;on to the sol;d carr;er, from 0 to 5 X of a ~etting agent, from 3 to 10 X of a d;spers;ng agent and, ~here necessary, from 0 to 10 % of one or more stab;l;sers and/or other add;t-;ves, such as penetrat;ng agents, adhes;ves, ant;-cak;ng agents~ dyestuffs and the l;ke.
The follow;ng are examples of var;ous compositions of ~ettable powders: Example 12 - act;ve ;ngred;ent 50 - calc;um l;gnosulphonate ~deflocculant) 5 %
~23~7~
- isopropyl naphthalenesulphonate (anionic wetting agent) 1 X
- anticaking silica 5 ~
- kaolin (f;ller) 39 X
Example 13: 70% strength we-ttable powder:
- act;ve ingredient 700 9 - sod;um dibutylnaphthylsulphonate 50 9 - 3:2:1 condensation product of naphthalene-sulphonic acid, phenylsulphonic acid and formaldehyde 30 9 - kaolin 100 9 - champagne chalk 120 9 Example 14: 40% strength wettable powder:
- act;ve ingredient 400 9 15 - sodium lignosulphonate 50 9 - sodium dibutylnaphthalene sulphonate 10 9 - sil;ca 540 9 Example 15: 25% strength wettable powder:
- actiYe ;ngredient 250 9 20 - calc;um lignosulphonate 45 9 - mixture of equal parts by ~eight of champagne chalk and hydroxyethylcellulose 19 9 - sodium dibutylnaphthalene sulphonate 15 9 - silica 195 9 25 - champagne chalk 195 9 - kaolin 281 9 Example 16: 25% strength we-ttable powder:
1 ~ 3 1 7 1 ~
- act;ve ;ngred;ent 250 g - isooctylphenoxy-polyoxyethylene-ethanol 25 9 - m;xture of equal parts by we;ght of champagne chalk and hydroxyethylcellulose 17 9 - sod;um aluminos;l;cate 543 9 - k;eselguhr 1o5 9 Example 17: 10% strength wettable powder:
- act;ve ;ngred;ent 100 9 lO - m;xture of sod;um salts of saturated fatty ac;d sulphates 30 9 - condensat;on product of naphthalene-sulphon;c acid and formaldehyde 50 9 - kaol;n 820 9 To obta;n these wettable powders, the act;ve ;ngred;ent is ;nt;mately m;xed w;th the add;t;onal sub-stances ;n su;table m;xers and the mixture ;s ground in m;lls or other su;table gr;nders. Th;s g;ves powders of advantageous wettability and suspendability; they can be suspended ;n wa~er at any desired concentration and th;s suspension can be used very advantageously, in part;cular for appl;cat;on to the leaves of the plants.
As already stated, the aqueous dispers;ons and aqueous emulsions, e.g. compos;t;ons obta;ned by d;luting, with water~ a wettable powder or an emulsifiable concen-trate accord;ng to the ;nvent;on, are ;ncluded within the general scope of the present ;nvent;on. The emuls;ons 1 23 J 7 ~ ~
can be of the water~;n-oil or o;l-;n-water type and they can have a th;ck cons;stency such as that of a "mayonna;se".
The granules, wh;ch are ;ntended to be placed on the so;l~ are usually prepared so as to have d;mens;ons 5 -of bet~een 0.1 and 2 mm, and they can be manufactured by agglomerat;on or ;mpregnat;on. In general, the granules conta;n 0.5 to 25X of act;ve ;ngred;ent and 0 to 10X of add;t;ves, such as stab;l;sers, slow release mod;f;ers, b;nders and solvents.
The compound of the formula ~I) can also be used ;n the form of dust;ng po~ders; ;t ;s also possible to use a compos;tion contain;ng 50 9 of act;ve ;ngred;ent and 950 9 of talc; it ;s also poss;ble to use a compos;-t;on conta;n;ng 20 9 of act;vP ;ngred;ent, 10 9 of f;nely 15 d;v;ded S;l;C3 and 970 9 of talc; these const;tuents are m;xed and ground and the m;xture ;s appl;ed by dust;ng.
"ACARICIDAL ESTER OF TRICYCLOHEXYL-TIN HYDROXIDE"
The present invention relates to a new organic derivative of tin, a method for its preparation,insecticidal and acaricidal compositions containing this derivative and a method of treating plants with these compositions to protect them from phytophagous insects and acarids.
Tricyclohexyl-tin hydroxide, better known by its common name cyhexatin, is a known acaricide which is noteworthy for its specific activity against phytophagous acarids, in particular in arboriculture and in the 10 cultivation of vegetables and ornamental plants. This product is used in the form of a wettable powder and, more recently, an emulsifiable concentrate. However, this latter formulation is difficult to prepare because of the -insolubility of cyhexatin in most of the usual solvents used 15 in agrochemistry. Complicated emulsifier systems, which do not ensure that the formulation has a completely satisfactory stability, have thus had to be used.
The present invention provides a new organic derivative of tin, which also has an excellent acaricidal 20 activity and moreover, surprisingly, can very easily be formulated in the form of an emulsifiable concentrate because of its remarkable solubility in the usual solvents used in agrochemistry.
The new organic derivative of tin according to 25 the present invention is tricyclohexyl-tin benzoate.
1 2 3 1 7 ~ B
The present invention also provides acaricidal compositions containing this product as the active ingredient, and in particular emulsifiable concentrates, which can be used to treat plants against phytophagous acarids.
Tricyclohexyl-tin benzoate has the formula:
( O ) - Sn - 0 - ~ - ~ (I) It can be prepared, for example, by reacting benzoic acid on tricyclohexyl-tin hydroxide. This reaction is carried out in an inert organic solvent medium, such as toluene, xylene, chlorobenzene, polychlorobenzene or cyclohexanone, at a temperature of, in general, at most 60C. The water formed in the course of the reaction is preferably removed at the rate at which it is formed, for example by absorption with a water-soluble salt, such as sodium sulphate or magnesium sulphate, or by azeotropic distillation of the solvent/water mixture.
The isolated product obtained is in the form of a white crystalline powder of melting point 111C.
The following non-limitative examples illustrate the invention.
i ~ 3 ~
i Example 1 A 20 l;tre reactor ;s charged with tr;cyclohexyl-tin hydrox;de (2"326 9, 6.04 mol), anhydrous toluene (9 l;tres) and benzo;c ac;d t737 9, 6.04 mol). The mix-5 ture ;s heated at about 50 - 60C, w;th st;rr;ng, for 1 hour 30 m;nutes and cooled to room temperature. Anhydrous sod; um sulphate (1,500 9) ;s then added and st;rr;ng ;s cont;nued for 1 hour The mixture ;s f;ltered and the f;ltrate ;s concentrated under redused pressure (6 mm Hg =
lO 789 Pa) at 50C. A wh;te sol;d product prec;pitates and ;s recrystall;sed ~rom hexane t3,250 ml) at 50C. The pro~
duct prec;p;tates by cooling to 10 - 15C. It ;s dr;ed and r;nsed ~;th cold hexane (750 ml). After dry;ng ;n a dry-;ng oven at 30C under reduced pressure t6 mm Hg = 789 Pa), 15 tr;cyclohexyl-t;n benzoate (2,185 g) ;s thus obta;ned.
~he hexane f; ltrate ;s concentrated and a second portion of product (362 9) is obta;ned.
- Total weight obta;ned: 2,547 9 - Y;eld: 36.8 X
20 ~ Melt;ng point: 111C
The structure shown ;s conf;rmed by analys;s by ;nfrared and proton NMR spectrometry.
Example 2 An emuls;f;able concentrate hav;ng the follow;ng 25 compos;t;on, for one l;tre of formulation, is prepared:
i23`17~
.
- tricyclohexyl-t;n benzoate 411 9 - calc; um dodecylbenzenesulphonate ;n 60X strength solution in isopropanol 50 - a 30 - 33: 1 ethylene ox;de/castor o;l condensate 50 9 - xylene 498 9 specif;c gravity at 20C: 1.008 Example 3 A reactor is charged, with cycloh~xanone (546 9) lO and 94 % pure tricyclohexyl-tin hydroxide (316 9) at 50C, w;th st;rring. The t;n derivat;ve does not dissolve.
Benzo;c ac;d (95 9) ;s then added and the temperature ;s kept at 50C. After st;rr;ng for 10 m;nutesr a yellow solut;on ;s obta;ned ~h;ch, after f;ltration and drying, 15 gives a clear solut;on. An emuls;f;able concentrate of spec;f;c grav;ty 1.057 at 20C ;s obta;ned by add;ng emuls;f;ers as ;n the preced;ng example.
Example 4 By proceeding as described in Example 2,a similar 20 emulsifiable concentrate is prepared, starting from the follow;ng m;xture:
- tr;cyclohexyl-t;n benzoate 411 9 - acetophenone 285 9 - xylene 279 9 - calc; um dodecylbenzenesulphonate ;n 60X strength solut;on ;n ;sopropanol 50 9 - ` !233716 - a 30 - 33 : 1 ethylene oxide/castor oil condensate 50 9 An emul~ifiable concentrate of specific gravity 1.075 at 20C is obtained.
5 Exa_ple 5 Acaricidal tests Bean plants at the stage of 1 trifoliate leaf are contaminated with a mixed population of Tetranychus urticae.
After 48 hours, the contaminated plants are lO treated with aqueous dilutions of the compositions to be tested, using a spray gun of the FISCHER type, until dripping wet. These compositions consist ofo a) for reference, a commercial composition PLICTRAN 600 F*, i.e. a concentrated aqueous suspension of 600 g/litre of 15 cyhexatin, and b) the emulsifiable concentrate according to the invention obtained in Example 3.
Three bean plants are used per product and per dose. The treated plants are kept in a greenhouse for 14 20 days (temperature 20-25C, relative humidity 40-60~, illumination 5 to lO,OOC lux). The plants are watered at the foot, to avoid any washing off of the products.
After 2, 7 and 14 days after the treatmentJ the population of acarids present on each plant is estimated in 25 relation to the mean of 3 controls treated only with water.
A percentage activity is deduced therefrom:
* Registered Trade Mark.
.....
1 ~ 3 ~ 7 J ~
Population on the treated plant Example: 100 X ~ in %
Populat;on on the untreated plant Under these conditions, the results shown in the following table are found:
X activity at Act;ve ingredient n days Product in g/hl 2 7 14 lO Reference 15 70 90 100 Invention 15 80100 100 15 Control 0 0 0 0 Furthermore, no phytotoxicity was found.
If the test is carr;ed out ;n the same manner on another species of acarids, Polyphagotarsonemus, it is found that the lethal dose at 90X, in ppm, ;s 10 for tri-20 cyclohexyl-t;n benzoate, ;.e. eight times less than that for the reference cyhexatin (used as a wettable powder).
Example 6: Insect;c;dal test D;scs of leaf from turnip plants are placed in gelose in Petri dishes. In each dish, 10 Plutella xyli-25 stella larvae are placed on each disc and the dish is J 2 3~ 7 1 6 covered with a ventilated lid. The product to be tested isdissolved in a water~acetone 50/50 mixture and Lhe discs are treated by spr~ying with this solution by usin~ a Potter tower at a dose equivalent to 675 litres/haO The discs S are kept at 26C. After48 hours after the treatmer,t, the l;ve and dead larvae are counted and the mortal;ty percent-age ;s calculated.
Under these conditions, it is found that tricyclo-hexyl-tin benzoate causes a mortality of at least 95% at 10 a dose of 100 g/hl, whilst cyhexatin, taken as a reference in the form of a wettable powder, is virtually inactive (less than 10%) at the same dose.
These examples clearly show:
the remarkable solubility of the compound according to the 15 invention which enables it to be easily introduced into formulations of the emuls;fiable concentrate type and enables it to be combined with other active ingred;ents of agrochem;stry, the excellent acaricidal activity of the compound accord-20 ing to the invention, which is more mult;valent than thereference, and a complementary insecticidal activity which the reference does not possess.
This compound can thus be used to combat ;nsects, 25 and more particularly phytophagous acarids, in crops such as, in part;cular, vineyards, arboriculture, vegetable crops and ornamental plants.
J ~ ~11 7 1 6 It is advantageously applied at application rates of O.05 to 5 kg/ha, preferably 0.1 to 2 kg/ha.
For its use in practice, the compound according to the invention is rarely employed by itself. Most frequently, it is used in compositions. These eompositions, which can be used to proteet plants from fungicidal diseases, eontain, as the aetive ingredient, the compound according to the invention as deseribed above in eombination with solid or liquid earriers whieh are acceptable in agricultural and/or sur~aee-aetive agen~ which are also acceptable in agriculture. In partieular, the usual inert carriers and the usual surface-active agents can be used.
These compositions can also contain any other type of ingredient, sueh as, for example, proteetive colloids, -adhesives, thickeners, thixotropie agents, penetration agents, stabilisers, sequestering agents and the like, as well as other known aetive ingredients with pesticidal properties (in partieular fungieides or, more espeeially, inseetieides) or with plant growth-promoting properties (in partieular fertilizers) or with plant growth-regulating properties. More generally, the eompounds aeeording to the invention ean be eombined with all solid or liquid additives in aecordanee with the eonventional teehniques of formulation.
In general, eompositions eontaining 0.5 to 5,000 ppm of active substanee are very suitable; these values are given for ready-to-use eompositions. "ppm" means v:~
1~1716 "parts per m;ll;on"D The range from 0.5 to 5,000 ppm corresponds to a range of from 5 x 10 5 X to 0.5 X (per-centages by weight).
As regards compositions su;table for storage and transportat;on, these more advantageously conta;n 0.5 to 95X (by we;ght) of act;ve substance.
The compos;tions to be used in agriculture accord-ing to the ;nvent;on can thus contain the act;ve ;ngred-;ents accord;ng to the ;nvent;on w;th;n very w;de limits, lO ;.e. of from 5.10 5 X to 95X (by we;ght).
In accordance w;th the above statements, the com-pounds according to the ;nvent;on are generally comb;ned with carr;ers and, ;f appropr;ate~ surface-active agents.
In the present account, the term "carrier" denotes 15 an organic or ;norgan;c, natural or synthet;c material with which the active ingredient ;s comb;ned in order to ~acil;tate its app~ication to the p~ant, to seeds or to the soil. This carrier is therefore generally inert and it must be acceptab~e in agriculture, in particular on 20 the plant treated. The carrier can be solid (clays, natural or synthet;c sil;cates, s;l;ca, res;ns, waxes, sol;d fert;l;sers and the l;ke) or l;qu;d (water, alcoholsr ketones, petroleum fractions, aromat;c or paraffinic hydrocarbons, chlorohydrocarbons, liquefied gases and the 25 l;ke).
The surface-active agent can be an emulsify;ng, d;spers;ng or wetting agent of the ion;c or non-;on;c 7 ~ ~
~ 10 --type. Examples which may be ment;oned are polyacryLic acid salts, lignosuLphonic acid salts, phenylsulphonic or naphthalenesulphonic acid salts, polycondensates of ethylene o~ide w;th fatty alcohols, fatty acids or fatty amines, subst;tuted phenols (in particular aLkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (in particular alkyltaurates) and phosphoric acid esters of polycondensates of ethylene oxide with alcohoLs or phenoLs. The presence of at least one surface-active agent is generally essential, ;f the active ingredient and/or the inert carrier are not soluble in water and if the veh;cle of appLication is ~ater.
For its application, the compound of the invent;on is thus generally in the form of compositions; these com-positions according to the invention are themselves in a fairly wide variety of solid or liquid forms.
As forms of sol;d compos;t;ons, there may be men-tioned powders for dusting or d;spersion ~with a content of compound of the formula (I) which can range up to 1û0%) and granules, ;n particular those obtained by extrusion, by compact;ng, by impregnation on a granular carrier or by granulation of a powder (the content of compound of the formula (I) in these granules is between 1 and 80%
in the latter cases).
As forms of Liquid compositions or compositions which are to be made up into liquid compositions on 1 2 ~ 1 7 ~ E
:
appl;cat;on, there may be mentioned solut;ons, in particu-lar emuLs;f;able concentrates, ultra-low volume (or ULV) formulat;ons~ emuls;ons, suspens;on concentrates, aerosols, wettable powders tor spray;ng powder) and pastes.
The emuls;f;able concentrates most frequently compr;se 10 to ~OX of act;ve ;ngred;ent, and the ready-to-use emuls;ons or solut;ons conta;n 0.01 to 20% of act-;ve ;ngred;ent~ In add;t;on to the solvent, the emuls;-f;able concentrates may conta;n, where necessary, 2 to 10 ~0% of su;table addit;ves, such as stab;~;sers, surface-act;ve agents, penetrating agents, corrosion inh;b;tors~
dyestuffs and adhes;vesO The follow;ng ;s an example of the compos;t;on of some concentrates: Exam~le 7 - act;ve ;ngred;ent 400 g/litre 15 - alkal; metal dodecylbenzenesulphonate 24 g/litre - 10 : 1 ethylene oxide/nonylphenol condensate 16 g/litre - cyclohexanone 200 g/l;tre - aromat;c solvent q.s.p. 1 litre 20The follow;ng are used in another formulat;on of an emuls;f;able concentrate: ExamE~le 8 - active ;ngredient 250 9 - epoxid;sed vegetable o;l 25 9 - m;xture of alkylaryl sulphonate and a 25 polyglycol/fatty alcohol ether100 9 - d;methylformamide 50 9 - xylene 575 9 1 ~ 3 ~
The following are used in another formulation of an emuls;fiable concentrate:~xam ~
- act;ve ingredient 450 9 - condensat& of ethylene ox;de w;th tr;styrylphenol 50 9 - alkali metal dodecylbenzenesulphonate 50 9 - chlorobenzene q.s.p. 1 litre From these concentrates, emuls;ons of any des-ired concentration can be obta;ned by d;lut;on ~;th water, these being part;cularly su;tabLe for appl;cation to the leaves.
For application called "ultra-low volume" (U.L.V.) w;th a spray of very f;ne droplets, solut;ons ;n organ;c solvents contain;ng 70 to 99 % oF act;ve ;ngredient are 15 prepared.
An ultra low volume formulat;on ;s prepared, for example, ~ith the following composition: Example 10 - act;ve ingre~;ent 200 9 - paraff;n;c/aromat;c o;l 200 9 20 - aromat;c solvent q.s.p. 1 l;tre The follow;ng is another ultra-low volume formul-at;on Example 11 .
- tr;cyclohexyl-t;n benzoate 150 9 - cypermethr;n 30 9 25 - tr;azophos 125 9 - paraffinic/aromatic oil 150 9 - betapinene 19 9 ~3~L7~L~
! . - 13 - acet;c anhydr;de 15 3 - cyclohexanone q.s.p. 1 litre The suspension concentrates, which can also be appl;ed by spraying are prepared so as to g;ve a stable fluid product wh;ch does not form a depos;t~ and they usually conta;n from 10 to 75 X of act;ve ;ngred;ent, from ~.5 to 15 % of surface-act;ve agents, from 0.1 to 10X of th;xotrop;c agents, from 0 to 10 X of su;table add;t;ves, such as ant;-foam agents, corros;on ;nh;b;tors, stabil;sers, penetrat;ng agents and adhes;ves, and, as the carr;er, water or an organic liqu;d ;n ~h;ch the act-;ve ;ngred;ent ;s spar;ngly soluble or ;nsoluble: certa;n sol;d organ;c substances or ;norgan;c salts can be d;s-solved ;n tne carr;er ;n order to ass;st ;n prevent;ng sed;-~5 mentat;on or to act as ant;-freeze agents for the water.
The wettable po~ders (or spray;ng powder) are usually prepared so as to conta;n 20 to g5% of act;ve ;ngredient, and they usually conta;n, ;n addit;on to the sol;d carr;er, from 0 to 5 X of a ~etting agent, from 3 to 10 X of a d;spers;ng agent and, ~here necessary, from 0 to 10 % of one or more stab;l;sers and/or other add;t-;ves, such as penetrat;ng agents, adhes;ves, ant;-cak;ng agents~ dyestuffs and the l;ke.
The follow;ng are examples of var;ous compositions of ~ettable powders: Example 12 - act;ve ;ngred;ent 50 - calc;um l;gnosulphonate ~deflocculant) 5 %
~23~7~
- isopropyl naphthalenesulphonate (anionic wetting agent) 1 X
- anticaking silica 5 ~
- kaolin (f;ller) 39 X
Example 13: 70% strength we-ttable powder:
- act;ve ingredient 700 9 - sod;um dibutylnaphthylsulphonate 50 9 - 3:2:1 condensation product of naphthalene-sulphonic acid, phenylsulphonic acid and formaldehyde 30 9 - kaolin 100 9 - champagne chalk 120 9 Example 14: 40% strength wettable powder:
- act;ve ingredient 400 9 15 - sodium lignosulphonate 50 9 - sodium dibutylnaphthalene sulphonate 10 9 - sil;ca 540 9 Example 15: 25% strength wettable powder:
- actiYe ;ngredient 250 9 20 - calc;um lignosulphonate 45 9 - mixture of equal parts by ~eight of champagne chalk and hydroxyethylcellulose 19 9 - sodium dibutylnaphthalene sulphonate 15 9 - silica 195 9 25 - champagne chalk 195 9 - kaolin 281 9 Example 16: 25% strength we-ttable powder:
1 ~ 3 1 7 1 ~
- act;ve ;ngred;ent 250 g - isooctylphenoxy-polyoxyethylene-ethanol 25 9 - m;xture of equal parts by we;ght of champagne chalk and hydroxyethylcellulose 17 9 - sod;um aluminos;l;cate 543 9 - k;eselguhr 1o5 9 Example 17: 10% strength wettable powder:
- act;ve ;ngred;ent 100 9 lO - m;xture of sod;um salts of saturated fatty ac;d sulphates 30 9 - condensat;on product of naphthalene-sulphon;c acid and formaldehyde 50 9 - kaol;n 820 9 To obta;n these wettable powders, the act;ve ;ngred;ent is ;nt;mately m;xed w;th the add;t;onal sub-stances ;n su;table m;xers and the mixture ;s ground in m;lls or other su;table gr;nders. Th;s g;ves powders of advantageous wettability and suspendability; they can be suspended ;n wa~er at any desired concentration and th;s suspension can be used very advantageously, in part;cular for appl;cat;on to the leaves of the plants.
As already stated, the aqueous dispers;ons and aqueous emulsions, e.g. compos;t;ons obta;ned by d;luting, with water~ a wettable powder or an emulsifiable concen-trate accord;ng to the ;nvent;on, are ;ncluded within the general scope of the present ;nvent;on. The emuls;ons 1 23 J 7 ~ ~
can be of the water~;n-oil or o;l-;n-water type and they can have a th;ck cons;stency such as that of a "mayonna;se".
The granules, wh;ch are ;ntended to be placed on the so;l~ are usually prepared so as to have d;mens;ons 5 -of bet~een 0.1 and 2 mm, and they can be manufactured by agglomerat;on or ;mpregnat;on. In general, the granules conta;n 0.5 to 25X of act;ve ;ngred;ent and 0 to 10X of add;t;ves, such as stab;l;sers, slow release mod;f;ers, b;nders and solvents.
The compound of the formula ~I) can also be used ;n the form of dust;ng po~ders; ;t ;s also possible to use a compos;tion contain;ng 50 9 of act;ve ;ngred;ent and 950 9 of talc; it ;s also poss;ble to use a compos;-t;on conta;n;ng 20 9 of act;vP ;ngred;ent, 10 9 of f;nely 15 d;v;ded S;l;C3 and 970 9 of talc; these const;tuents are m;xed and ground and the m;xture ;s appl;ed by dust;ng.
Claims (8)
1. Tricyclohexyl-tin benzoate.
2. A process for the preparation of the compound according to claim 1, which comprises reacting tricyclohexyl-tin hydroxide with benzoic acid in an inert organic solvent medium.
3. A process according to claim 2, wherein the water formed during the reaction is removed as it is formed.
4. An insecticidal or acaricidal composition which comprises, as the active ingredient, the compound according to claim 1 in association with one or both of (a) a solid or liquid carrier which is acceptable in agriculture and (b) a surface-active agent which is acceptable in agriculture.
5. A composition according to claim 4, which also comprises an insecticide.
6. A composition according to claim 4, which is in the form of an emulsifiable concentrate.
7. A method of preventing damage to plants caused by phytophagous insects and acarids, which comprises applying to the plants a composition according to any one of claims 4 to 6.
8. A method of preventing damage to plants caused by phytophagous insects and acarids, which comprises applying to the plants a composition according to any one of claims 4 to 6 at a rate such as to give an application rate of tricyclohexyl-tin benzoate of 0.05 to 5 kg/ha.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8304884A FR2543142B1 (en) | 1983-03-22 | 1983-03-22 | ESTER OF TRICYCLOHEXYLETAIN ACARICIDE HYDROXIDE |
| FR8304884 | 1983-03-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1231716A true CA1231716A (en) | 1988-01-19 |
Family
ID=9287208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000449971A Expired CA1231716A (en) | 1983-03-22 | 1984-03-20 | Acaricidal ester of tricyclohexyl-tin hydroxide |
Country Status (24)
| Country | Link |
|---|---|
| US (1) | US4602945A (en) |
| JP (1) | JPS59176296A (en) |
| KR (1) | KR840007808A (en) |
| AU (1) | AU2591984A (en) |
| BE (1) | BE899225A (en) |
| BR (1) | BR8401318A (en) |
| CA (1) | CA1231716A (en) |
| CH (1) | CH660365A5 (en) |
| DE (1) | DE3410064A1 (en) |
| DK (1) | DK136284D0 (en) |
| ES (1) | ES8506034A1 (en) |
| FR (1) | FR2543142B1 (en) |
| GB (1) | GB2136811B (en) |
| GR (1) | GR81825B (en) |
| HU (1) | HUT33961A (en) |
| IL (1) | IL71165A0 (en) |
| IT (1) | IT1177597B (en) |
| LU (1) | LU85259A1 (en) |
| NL (1) | NL8400893A (en) |
| NZ (1) | NZ207559A (en) |
| OA (1) | OA07683A (en) |
| PH (1) | PH20025A (en) |
| PT (1) | PT78291B (en) |
| ZA (1) | ZA842064B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4732456A (en) * | 1984-08-28 | 1988-03-22 | Taliq Corporation | Scattering display for contrast enhancement including target |
| US4832458A (en) * | 1984-08-28 | 1989-05-23 | Talig Corporation | Display for contrast enhancement |
| US8110608B2 (en) | 2008-06-05 | 2012-02-07 | Ecolab Usa Inc. | Solid form sodium lauryl sulfate (SLS) pesticide composition |
| US8968757B2 (en) | 2010-10-12 | 2015-03-03 | Ecolab Usa Inc. | Highly wettable, water dispersible, granules including two pesticides |
| CN103396437B (en) * | 2013-07-22 | 2015-09-09 | 衡阳师范学院 | Two (Tricyclohexyltin) dicarboxylic esters and preparation method and application |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL96805C (en) * | 1957-11-18 | 1900-01-01 | ||
| NL269911A (en) * | 1960-10-04 | 1900-01-01 | ||
| US3129236A (en) * | 1960-12-31 | 1964-04-14 | Monsanto Chemicals | Bis(trihydrocarbyl tin oxy) aromatic compounds |
| NL299805A (en) * | 1962-10-29 | 1900-01-01 | ||
| US3264177A (en) * | 1964-02-17 | 1966-08-02 | Dow Chemical Co | Methods for the control of arachnids |
| US3542824A (en) * | 1968-07-31 | 1970-11-24 | Dow Chemical Co | Perfluorocarboxylic acid ester of tricyclohexyltin hydroxide |
| US3598849A (en) * | 1968-09-20 | 1971-08-10 | Dow Chemical Co | Tricyclohexyltin esters |
| US3703588A (en) * | 1969-11-21 | 1972-11-21 | Norio Saito Nara Ken And Uniti | Method for imparting antistatic properties to polymeric materials |
| US3861949A (en) * | 1971-04-27 | 1975-01-21 | Kureha Chemical Ind Co Ltd | Article having applied to the surface thereof, an anti-fouling composition comprising a polymer and an organo-tin compound |
| US3790611A (en) * | 1972-10-05 | 1974-02-05 | M & T Chemicals Inc | Tris(cyclohexylalkyl)tin or hexakis(cyclohexylalkyl)tin compounds |
| DE2419208A1 (en) * | 1974-04-18 | 1975-11-06 | Schering Ag | PRODUCTS WITH SELECTIVE, HERBICIDAL AND ALGICIDAL EFFECTS |
| FR2335514A1 (en) * | 1975-12-17 | 1977-07-15 | M & T Chemicals Inc | Triorgano-tin derivs. of unsatd. acids prodn. - by reacting acid and tin (hydr)oxides in presence of drying agents, for use in making polymers (DK 9.8.76) |
| US4224338A (en) * | 1976-08-17 | 1980-09-23 | The Dow Chemical Company | Simultaneous fungicidal and miticidal protection of plants employing certain tin compounds |
-
1983
- 1983-03-22 FR FR8304884A patent/FR2543142B1/en not_active Expired
-
1984
- 1984-02-29 DK DK1362/84A patent/DK136284D0/en not_active Application Discontinuation
- 1984-03-06 IL IL71165A patent/IL71165A0/en unknown
- 1984-03-14 GR GR74100A patent/GR81825B/el unknown
- 1984-03-19 PH PH30411A patent/PH20025A/en unknown
- 1984-03-19 KR KR1019840001392A patent/KR840007808A/en not_active Application Discontinuation
- 1984-03-19 DE DE19843410064 patent/DE3410064A1/en not_active Withdrawn
- 1984-03-20 CA CA000449971A patent/CA1231716A/en not_active Expired
- 1984-03-20 NZ NZ207559A patent/NZ207559A/en unknown
- 1984-03-20 GB GB08407153A patent/GB2136811B/en not_active Expired
- 1984-03-20 ZA ZA842064A patent/ZA842064B/en unknown
- 1984-03-20 AU AU25919/84A patent/AU2591984A/en not_active Abandoned
- 1984-03-20 IT IT47894/84A patent/IT1177597B/en active
- 1984-03-21 ES ES530812A patent/ES8506034A1/en not_active Expired
- 1984-03-21 PT PT78291A patent/PT78291B/en unknown
- 1984-03-21 HU HU841132A patent/HUT33961A/en unknown
- 1984-03-21 LU LU85259A patent/LU85259A1/en unknown
- 1984-03-21 NL NL8400893A patent/NL8400893A/en not_active Application Discontinuation
- 1984-03-21 CH CH1438/84A patent/CH660365A5/en not_active IP Right Cessation
- 1984-03-21 JP JP59054120A patent/JPS59176296A/en active Pending
- 1984-03-21 BR BR8401318A patent/BR8401318A/en unknown
- 1984-03-22 OA OA58257A patent/OA07683A/en unknown
- 1984-03-22 US US06/592,353 patent/US4602945A/en not_active Expired - Fee Related
- 1984-03-22 BE BE0/212613A patent/BE899225A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| AU2591984A (en) | 1984-09-27 |
| ES530812A0 (en) | 1985-06-16 |
| GR81825B (en) | 1984-12-12 |
| NL8400893A (en) | 1984-10-16 |
| IT8447894A1 (en) | 1985-09-20 |
| IT8447894A0 (en) | 1984-03-20 |
| CH660365A5 (en) | 1987-04-15 |
| PT78291B (en) | 1986-08-08 |
| ES8506034A1 (en) | 1985-06-16 |
| DE3410064A1 (en) | 1984-09-27 |
| PH20025A (en) | 1986-09-04 |
| KR840007808A (en) | 1984-12-11 |
| GB8407153D0 (en) | 1984-04-26 |
| LU85259A1 (en) | 1985-10-14 |
| BE899225A (en) | 1984-09-24 |
| PT78291A (en) | 1984-04-01 |
| IL71165A0 (en) | 1984-06-29 |
| FR2543142B1 (en) | 1986-01-03 |
| GB2136811B (en) | 1986-07-09 |
| OA07683A (en) | 1985-05-23 |
| DK136284D0 (en) | 1984-02-29 |
| GB2136811A (en) | 1984-09-26 |
| IT1177597B (en) | 1987-08-26 |
| HUT33961A (en) | 1985-01-28 |
| ZA842064B (en) | 1984-10-31 |
| FR2543142A1 (en) | 1984-09-28 |
| NZ207559A (en) | 1985-12-13 |
| US4602945A (en) | 1986-07-29 |
| JPS59176296A (en) | 1984-10-05 |
| BR8401318A (en) | 1984-10-30 |
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